Durably shaping keratinous fibrous materials

ABSTRACT

Durable shaping of keratinous fibrous materials by impregnation with solutions or dispersions of compounds which in the betaine form have the formula R1R4R5N -CHR2-CHR3-O-SO2 wherein R1 is an unsubstituted or substituted hydrocarbon radical, R2 and R3 each denotes a hydrogen atom or a lower alkyl radical, and R4 and R5 each denotes a hydrogen atom or an unsubstituted or substituted hydrocarbon radical and heating with steam at 100* to 150* C while shaping; fibrous materials thus treated.

United States Patent Widder et a1.

[54] 'DURABLY SHAPING KERATINOUS FIBROUS MATERIALS [72] Inventors: RudiWidder, Eppelheim; Harry Distler,

Ludwigshafen; Erwin Haug, Gruenstadt, allof Germany [73] Assignee:Badische Anilin-& Soda-Fabrik Aktiengesellschaft, Ludwigshafen/Rhine,Germany [22] Filed: July 28, 1969 [21] Appl. No.: 845,508

[30] Foreign Application Priority Data July 27, 1968 Germany ..P 17 69865.6

[52] [1.8. Ci ..l17/119.8, 8/127.6,117/1l;139.4;65.2, 117/141 [51] Int.Cl. ..B44d l/48, D06n 13/36 [58] FieldofSearch..ll7/14l,119.8,140R,139.7, 117/135.5, 63, 69; 260/501.l2; 8/127.6, 128

[56] References Cited UNITED STATES PATENTS 3,055,774 9/1962 Gilkey etal ..117/139.4 X 3,059,990 10/1962 Koenig et al. ..1 17/141 X [451 May23, 1972 Primary Examiner-William D. Martin Assistant Examiner-Harry .l.Gwinnell Attorney-Johnston, Root, O'Keeffe, Keil, Thompson & ShurtleffABSTRACT Durable shaping of keratinous fibrous materials by impregnationwith solutions or dispersions of compounds which in the betaine formhave the formula RRRN CHR CHR?O- S0 wherein R is an unsubstituted orsubstituted hydrocarbon radical, R and R each denotes a hydrogen atom ora lower alkyl radical, and R and R each denotes a hydrogen atom or anunsubstituted or substituted hydrocarbon radical and heating with steamat 100 to 150 C while shaping; fibrous materials thus treated,

12 Claims, No Drawings DURABLY SHAPING KERATINOUS FIBROUS MATERIALS Itis known that fibrous material containing or consisting of keratin canbe durably shaped in the required manner by impregnating it with amercaptocarboxylic acid and then oxidizing it, or treating it withsteam, while shaping. This method has a number of disadvantages whichcomplicate or limit its use. For example, it is difficult to produceconsistent results; colored articles readily undergo color changes atthe treated places, and intensely red discoloration occurs when ironions are present; moreover, the treatment has to be carried out bygarment manufactures rather than by weavers.

For the last mentioned reason it has been desirable to provide a processwhich would enable weavers to sensitize fibrous material of the saidkind, i.e., impart to it the property, persisting for a prolongedperiod, of being capable of retaining indefinitely any shape imparted toit by simple measures. One method of achieving this aim which has beensuggested is to treat fibrous material of the said kind with sodium orammonium sulfite, a durable change of shape being obtained by shapingthe material while treating it with steam at elevated temperature.

This process, too, does not fully satisfy the processors requirements.The sensitization achieved in the first operation is lost again aftersome time, so that it is often impossible to keep the material in asensitized condition for sufficiently long periods on its way from thefinisher to the processor.

Salts of monoethanolamine have also been proposed for durable shaping ofkeratinous fibrous material. However, the effects obtainable are notsufficiently durable to laundering.

We have now found a method for the durable shaping of keratinous fibrousmaterial, e.g., yarn, non-woven fabrics, felts and preferably woven andknitted fabrics, as well as textiles prepared therefrom, particularlygarments, of wool or other animal fibers, which method does not have thesaid disadvantages.

The method of the invention comprises impregnating fibrous material withan aqueous solution or dispersion of a compound-which in the betaineform has the general formula where R is an unsubstituted or substitutedhydrocarbon radical, R and R are hydrogen atoms or lower alkyl radicalspreferably having from one to five carbon atoms, and R and R arehydrogen atoms or unsubstituted or substituted hydrocarbon radicalspreferably having from one to 20. carbon atoms, and heating theimpregnated materials with steam at 100 to 150 C while shaping, ifdesired after drying, intermediate storage and/or making it intogarments.

The radicals R, R and R in Formula I may be for example alkyl,cycloalkyl, aryl or aralkyl radicals having from one to 20 carbon atomswhich may bear substituents such as hydroxyl or alkoxyl groups. Exampleof suitable radicals are methyl, ethyl, Z-hydroxyethyl, propyl,2-hydroxypropyl, butyl, 2-ethylhexyl, octyl, dodecanyl, cyclohexyl,phenyl, tolyl, benzyl, methoxyethyl, ethoxyphenyl and 4-ethoxybutyl.

Among the compound to be used according to the invention those arepreferred in which the radical R contains up to carbon atoms, R and Rare hydrogen or methyl and R and R are hydrogen or aliphatic radicalshaving up to two carbon atoms.

The substances to be used for the purposes of the invention are shown inFormula I in the betaine form. Provided the radicals R and/or R are nothydrocarbon radicals, the substances may also be present in the form ofordinary salts in which the nitrogen atom has lost its positive chargeowing the elimination of a proton, and the negative charge of theresultant anion is compensated by a separate cation X The nature of thecation X has no appreciable effect on the suitability of the substancesto be used according to the invention. It may be for example an alkalimetal, ammonium or substituted ammonium ion, in particular one havingthe formula R-NH -R Whether the substances to be used according to theinvention are present in the impregnating liquor in the betaine form orin the form of a salt 11 or II] depends on the pH of the liquor, also ingenerally the case with dipolar ions.

Examples of compounds having the above general formulae are (Ilia Thecompounds of the general Formula I, 11 or 111 may be prepared forexample by the method described in U.S. Pat. application Ser. No.823,160, filed May 8, 1969, by Harry Distler et al. by reaction ofamines having the general formula with 1,2-glycol sulfites of thegeneral formula o o \s/ II where the radicals R to R have the meaningsgiven above.

The compounds of the general Formula I, II or II are used in the form oftheir aqueous solutions or dispersions, especially their aqueoussolutions. They are applied to the fibrous material in the usual manner,for example by knife coating, sprying, dipping or preferably by padding.It has been found advantageous to apply the solutions or dispersions atsuch a rate that 0.01 to 0.2 mole, preferably 0.02 to 0.1 mole, of acompound of the general Formula I, II or III is applied per kilogram ofmaterial to be treated.

It is sometimes expedient to add wetting agents to the impregnatingliquors in order to achieve rapid penetration and equal distribution ofthe ingredients. Non-ionic wetting agents are preferred. Wetting agentsare dispensible if the material has already been wetted in an earliertreatment.

The impregnating liquors may contain other ingredients conventionallyused for treating keratinous fibers, for example water and oilrepellents, such as silicones and compounds having perfluorinated carbonchains. After impregnation the fibrous material can be immediatelybrought into the desired shape in the presence of steam, if desiredafter intermediate drying. The special advantages of the new process arehowever particularly apparent when shaping is carried out later, becauseafter the said intermediate drying operation the impregnated materialcan be stored for very long periods without the sensitizing effectimparted by the impregnation being lost. Shaping can be carried out atany processing stage in the presence of steam, and the material willretain the shape imparted to it. It is possible to shape mechanically,for example by means of smooth or structured rollers, molds, platingpresses or goffering equipment, or manually, for example by ironing. Atany rate care must be taken to ensure that hot steam can act on thematerial while this is being treated. Temperatures between 100 and 150 Care used for shaping.

By the said method the fibrous material can for example be calendered,embossed, goifered, and particularly pleated and creased. The effectsobtained are highly durable, i.e., they are not lost in use or anycleaning operations.

Fabrics containing or consisting of keratin fibers, or garments made ofsuch material, can therefore be given an easycare finish. The process ofthe invention furthermore results in a substantial improvement in thehandle, and the presence in the fibrous material of unreacted compoundsof the general Formula I, II or 111 makes the material easier to shapein garment fabrication.

The new process can be applied with special advantage after ashrink-resist finishing operation, for example a treatment withoxidizing agents such as dichlorocyanuric acid or salts thereof.

The invention is further illustrated by the following examples in whichparts are by weight unless otherwise specified.

EXAMPLE 1 Made-up mens trousers of pure wool are sprayed with a percentaqueous solution of the compound of Formula VI at the places where theyare to be creased, until the sprayed portions have increased 40 50percent in weight. The trousers are then arranged in the press andtreated for to seconds with steam at 100 to 120 C while pressing to givethe desired creases. After the steam has been shut off, the trousers areleft in the press for another 20 to seconds, suction being applied for 5seconds to accelerate cooling.

The trousers obtained exhibit extremely durable creases.

EXAMPLE 2 Pure wool cloth (plain weave; 250 g/m is padded with a 5aqueous solution of the substance of Formula VII and squeezed to a wetpickup of 50 percent. The material is then decatized by treating it for5 minutes with saturated steam at 2 atm. gauge. Suction is applied for 3to 5 seconds and the cloth dried on a stenter with 3 percent overfeed at100 C. The cloth thus treated is distinguished by an improved hand, issmoother in appearance, and has improved crease behavior in the wetcondition and a durable decatizing effect.

EXAMPLE 3 Cloth of the type described in Example 2 is impregnated anddried as described in that example. It is then stored for 3 months andmade into trousers. It is found that the trousers are easier to shapethan trousers of the same material which has not been impregnated withthe substance of Formula VII. The trousers are steamed in an ironingpress in the way described in Example 1. They have sharp and verydurable creases and improved crease behavior in the wet condition.

EXAMPLE 4 Made-up men's trousers of pure wool are sprayed with a 5percent aqueous solution of the compound of Formula [V at the placeswhere they are to be creased, until the sprayed portions have increased40 50 percent in Weight. The trousers are then arranged in the press andtreated for 10 to 20 seconds with steam at to C while pressing to givethe desired creases. After the steam has been shut off, the trousers areleft in the press for another 20 to 30 seconds, suction being appliedfor 5 seconds to accelerate cooling.

The trousers obtained exhibit extremely durable creases.

EXAMPLE 5 Pure wool cloth (plain weave; 250 g/m) is padded with a 5percent aqueous solution of the substance of formula V and squeezed to awet pickup of 50 percent. The material is then decatized by treating itfor 5 minutes with saturated steam at 2 atm. gauge. Suction is appliedfor 3 to 5 seconds and the cloth dried on a stenter with 3 percentoverfeed at 100 C. The cloth thus treated is distinguished by animproved hand, is smoother in appearance, and has improved creasebehavior in the wet condition and a durable decatizing effect.

EXAMPLE 6 Cloth of the type described in Example 5 is impregnated anddried as described in that example. It is then stored for 3 months andmade into trousers. It is found that the trousers are easier to shapeand dress than trousers of the same material which has not beenimpregnated with the substance of F ormula V. The trousers are steamedin an ironing press in the way described in Example I. have sharp andvery durable creases and improved crease behavior in the wet condition.

EXAMPLE 7 Made-up men's trousers of pure wool are sprayed with a 5percent aqueous solution of the compound of Formula Vlll at the placeswhere they are to be creased, until the sprayed portions have increased40 50 percent in weight. The trousers are then arranged in the press andtreated for 10 to 20 seconds with steam at 100 to 120 C while pressingto give the desired creases. After the stem has been shut off, thetrousers are left in the press for another 20 to 30 seconds, suctionbeing applied for 5 seconds to accelerate cooling.

The trousers obtained exhibit extremely durable creases.

We claim:

1. A method of durably shaping keratinous fibrous material whichcomprises impregnating said fibrous material with an aqueous solution ordispersion of a compound which in the betaine form has the generalformula or salt thereof where R is an unsubstituted or substitutedhydrocarbon radical, R and R denotes a hydrogen atom or an unsubstitutedor substituted hydrocarbon radical, and heating the impregnated materialwith steam at 100 to C while shaping.

2. A method as claimed in claim 1 wherein the betaine compound used isone where R is an unsubstituted or substituted hydrocarbon radicalhaving up to 15 carbon atoms, and R and R each denotes a hydrogen atomor an alkyl radical having up to two carbon atoms.

3. A method of durably shaping keratinous fibrous material whichcomprises impregnating said fibrous material with an aqueous solution ordispersion of a compound which in the salt form has the general formulaor salt thereof, where R is an unsubstituted or substituted hydrocarbonradical with one to carbon atoms, R and R are hydrogen atoms or alkylradicals having from one to 5 carbon atoms, R and R are hydrogen atomsor unsubstituted or substituted hydrocarbon radicals having from one tocarbon atoms.

5. Keratinous fibrous material as claimed in claim 4 wherein the betainecompound used is one where R and R each denotes a hydrogen atom or analkyl radical having up to two carbon atoms.

6. Keratinous fibrous material which has been impregnated with a betainesalt having the formula where R is an unsubstituted or substitutedhydrocarbon radical, R and R each denotes a hydrogen atom or a loweralkyl radical, R denotes a hydrogen atom gr an unsubstituted orsubstituted hydrocarbon radical, and X is a cation.

7. Keratinous fibrous material as claimed in claim 6 wherein X is analkali metal, ammonium or substituted ammonium cation.

8. A method as claimed in claim 1 wherein said heating while shaping isconducted after drying of the impregnated keratinous fibrous material.

9. A method as claimed in claim 1 wherein said fibrous material is inthe form of a garment during said heating while shaping.

10. A method as claimed in claim 3 wherein X is an alkali metal,ammonium or substituted ammonium cation.

11. A method as claimed in claim 3 wherein R is a hydrogen atom.

12. Keratinous fibrous material as claimed in claim 6 wherein R is ahydrogen atom.

gt) u STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,66%,864 v I Dated May 23 4 19 72 Inventor) Rudi Widd'er, HarryDistler, and Erwin Haug It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 1, line 45, to the right of the formula, insert- I line 64,"compound" should read compounds line 67,

"R should read --R Column 2, line 19, "in-generally" should read' -Ygenerally --I;

line 67, "I, II or II" should read I, II, or III Column 4, line 37,"Example 1. have" should read 1 Example 1. They have --;lines 67 to 68,claim 1, "denotes a-hydrogen atom or an unsubstituted or substitutedhydrocarbon v radical" should read each denotes a hydrogen atom or alower alkyl radical, and R and R each denotes a hydrogen atom oranunsubstituted or substituted hydrocarbon radical -f-.

Signed and sealed this 5th day of'December 1972 v (SEAL) Attest:

EDWARD MQFLETCHERJR. I ROBERT GOTTSCHALK Attesting OfficerCommissionerof Patents

2. A method as claimed in claim 1 wherein the betaine compound used isone where R1 is an unsubstituted or substituted hydrocarbon radicalhaving up to 15 carbon atoms, and R2 and R3 each denotes a hydrogen atomor an alkyl radical having up to two carbon atoms.
 3. A method ofdurably shaping keratinous fibrous material which comprises impregnatingsaid fibrous material with an aqueous solution or dispersion of acompound which in the salt form has the general formula where R1 is anunsubstituted or substituted hydrocarbon radical, R2 and R3 each denotesa hydrogen atom or a lower alkyl radical, R4 denotes a hydrogen atom oran unsubstituted or substituted hydrocarbon radical and X+ is a cation,and heating the impregnated material with steam at 100* to 150* C whileshaping.
 4. Keratinous fibrous material which has been impregnated withan aqueous solution or dispersion of a compound which in the betaineform has the general formula or salt thereof, where R1 is anunsubstituted or substituted hydrocarbon radical with one to 15 carbonatoms, R2 anD R3 are hydrogen atoms or alkyl radicals having from one to5 carbon atoms, R4 and R5 are hydrogen atoms or unsubstituted orsubstituted hydrocarbon radicals having from one to 20 carbon atoms. 5.Keratinous fibrous material as claimed in claim 4 wherein the betainecompound used is one where R2 and R3 each denotes a hydrogen atom or analkyl radical having up to two carbon atoms.
 6. Keratinous fibrousmaterial which has been impregnated with a betaine salt having theformula where R1 is an unsubstituted or substituted hydrocarbon radical,R2 and R3 each denotes a hydrogen atom or a lower alkyl radical, R4denotes a hydrogen atom or an unsubstituted or substituted hydrocarbonradical, and X+ is a cation.
 7. Keratinous fibrous material as claimedin claim 6 wherein X+ is an alkali metal, ammonium or substitutedammonium cation.
 8. A method as claimed in claim 1 wherein said heatingwhile shaping is conducted after drying of the impregnated keratinousfibrous material.
 9. A method as claimed in claim 1 wherein said fibrousmaterial is in the form of a garment during said heating while shaping.10. A method as claimed in claim 3 wherein X+ is an alkali metal,ammonium or substituted ammonium cation.
 11. A method as claimed inclaim 3 wherein R4 is a hydrogen atom.
 12. Keratinous fibrous materialas claimed in claim 6 wherein R4 is a hydrogen atom.